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the cavity radii for the ions. The procedure developed in this
study reduced the error found in a previous technique for cyclic
amines by 62%.
1. Introduction
In order to satisfy environmental combustion standards, acid gases such as
CO2 and H2S must be removed from gaseous streams in refining, and in chemical
and gas associated production plants. Natural gas and synthetic fuels such as
coal gasification and shale oil cover broad ranges of both acid gas composition
and pressure (1). The most common solvents used to capture CO2 are the
alkanolamines such as the monoethanolamine (MEA), diethanolamine (DEA)
and n-methyldiethanol amine (MDEA). These amines are used commercially in
post-combustion CO2 capture as aqueous solution or in aqueous organic medium
or in combination with aqueous potassium carbonate solutions (2).
CO2 capture by chemical absorption using aqueous solution of amine uses
absorper abd stripper units. This technology needs to overcome the challenge
of reducing the energy, the environmental impact and the capture cost. Finding
a better solvent is the path to solve these issues. High cyclic capacity, fast
absorption rate, high equilibrium temperature sensitivity and low enthalpy of
absorption are some of the factors to be considered in the selection of the best
solvent. Both capital and capture costs of CO2 removal depend on the CO2
absorption and desorption rates. Solvents with fast reaction rates can reduce the
height of the packing required in both the absorber and stripper. Energy in the
stripper can be saved by faster solvents and by achieving a closer equilibrium
in the absorber (3). Since 1960, various primary, secondary and tertiary amines
were studied for their reaction rate with CO2 to find out faster solvents and many
studies were published in the literature, and reviewed by Blauwhoff et al. (4),
Versteeg et al. (5), and more recently by Vaidya et al. (6) In this work, a screening
study was performed on different types of amines (primary, secondary, tertiary,
cyclic and polyamines) using a well established stopped-flow procedure in order
to find the best solvents based on their kinetics rates at 298.15 K. Six cyclic
aqueous polyamines were studied at (298.15 to 313.15) K over a concentration
range of (20 to 120) molm-3.
The bascity of the solvent, quantified by the pKa of its conjugate acid, is
an important fundamental property which affects the kinetics and possibly the
mechanism of the capture process (36). A linear relationship between the pKa
of an acid or base with its catalytic effect on the reaction rate was reported by
Brnsted et al. (4) Many literature studies reported on a Brnsted relationship
between the rate constant of the reaction of amines with CO2 and the basicity of
such amines (48). The following Brnsted relationship was reported by Versteeg
et al. (5)for aqueous primary and secondary alkanolamines:
Because of the essential need for pKa values, it would be useful to predict the
aqueous pKa of new amines by a prior means. One direct way is the calculation
of such values using a widely popular quantum chemistry program (Gaussian
03) with a continum solvation model, in which the solvent is approximated as a
dielectric continuum. A study of this kind was reported by da Silva and Svendsen
(9), and improved by our previous work to predict the aqueous pKa values
within 1 (10). The procedure and the choice of conformers for the studied
alkanolamines were recently published.
2. Experimental Setup
2.1. Determination of Chemical Kinetics
A stopped flow technique was used for the direct measurement of pseudo
first-order kinetics, k0, for different aqueous and non-aqueous diamines, as well
as primary, secondary and tertiary alkanolamines. The experimental setup is
a standard SF-51 stopped flow unit from Hi-Tech Scientific Ltd., UK. It is an
assembly of four major units; a sample-handling unit, a conductivity-detection
cell, an A/D converter and a microprocessor. The sample-handling unit is
comprised of a stainless steel case which provides support and an enclosure for
the sample flow circuit. Schematics of the sample handling unit is shown in
Figure 1. The entire flow circuit, with the exception of the stop/waste syringe, is
enclosed in a thermostat and maintained at a constant temperature by an external
water bath within 0.1 K. The front panel of the sample handling unit displays a
temperature indicator with a resolution of 0.1 K and an air pressure indicator. A
pneumatic air supply is used to control the movement of drive plate located at the
bottom of the internal syringes that contains the CO2 solution and amine solution.
During an experimental run, a fresh solution of CO2 is loaded into one syringe
and a fresh solution of amine is loaded into the other.
CO2 solutions were prepared by bubbling research grade CO2 for at least
half an hour through the desired medium with water for an aqueous solution and
methanol or ethanol for a non-aqueous solution. The concentration of CO2 in the
liquid medium was measured in a gas chromatograph (GC-6890 from Agilent). It
was then diluted with the chosen media to keep the CO2 solution at least 10 times
lower than the amine solution in order to achieve pseudo first-order conditions.
The pseudo first-order rate constants of the aqueous solution of EDA obtained
for different concentrations are compared with previously published data (11)
in Figure 2. A reproducibility of 4% (absolute average deviation of 15 sets of
k0 values from their mean value) and an estimated uncertainty of 5% (absolute
average deviation of the obtained value from the literature value) were observed
when compared to published data. By fitting the empirical power-law kinetics
to the data of the experimentally found pseudo first order constants for CO2 as
shown in Figure 2, the reaction order of the amine was determined.
45
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Figure 2. Pseudo first order reaction for (EDA + H2O) solution. , 298.15 K; ,
298.15 K11; , 303.15 K; , 303.15 K11; , 308.15 K; , 308.15 K11; , 313.15 K;
, 313.15 K11; --- Power law kinetics.
46
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
where PZH+ represents the monoprotonated piperazine, and PZH22+ denotes the
piperazinium ion. Considering the mole fraction of water as unity and expressing
the concentration of hydronium ion, [H3O+], as [H+], the pKa values of PZ can be
written as:
The last terms in equations (5) and (6) are the thermodynamic corrections. The
calculation procedures were explained in Albert and Serjeant (12). 0.5 ml of the
titrant HCl was added to 50 mL solution of 0.01 M PZ in 10 parts (5ml) to calculate
the ratios of [PZH+]/[PZ] and the next 10 parts of 0.5 ml were added to find the
ratios of [PZH2 2+]/[PZH+]. The corresponding pH values after each addition of
titrant were recorded. These ratios were used in equations 5 and 6 to find pKa(1) and
pKa(2) values. Thermal corrections were subtracted from the pKa(1) values and the
average values were calculated as the first pKa of PZ. Correspondingly thermal
corrections for the second dissociation constants (pKa(2)) were deducted to find
the average value as the second pKa. The Debye-Hckel equation was used to
calculate the activity coefficients:
47
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
where the terms A and B are called the Debye-Hckel equation constants and vary
with the dielectric constant and the temperature of the solvent. zi is the ion valance
and the term ki is the ionic size parameter, i.e. the mean distance of approach
of the ions. I represents the ionic strength and depends on the concentration of
the solution. The values of A and B for different temperatures were taken from
Manov et al. (13) The ionic size parameters (ki) values were also obtained from the
literature (14). The calculation of the ionic strength follows different procedures
for the first and second pKas as shown in the work of Albert and Serjeant (13).
where kov is the overall reaction rate constant for CO2 loss, KB = k2ZkB/kb, and k2Z,
kb (b = backwards) and kB (B = base) are the elementary rate constants in steps (8)
and (9). B denotes any proton-accepting species present; if one considers {H2O,
OH-, HXYN}, then one has elementary rate constants kB = {kW, kOH, kHXYN} and
the corresponding composites KB in equation (10).
Equation (10) is very general and should cover most cases. Fitting this
equation to experimental data would give values for the three KBs as well as k2Z,
but this 4-parameter function often has indeterminacy problems. Danckwerts (15)
pointed out two limiting cases, arising if kb << BkB[B] [equation (11)] or kb >>
BkB[B] [equation (12)]:
48
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Equation (12), like (10), allows for fractional orders of the amine between 1 and 2.
An additional possibility for the CO2 loss rate could be the uncatalyzed reaction:
but this was deemed unimportant by Littel, Versteeg, and van Swaaij (19). They
went on to straightforwardly derive the rate expression from the termolecular
mechanism (14):
The value of KW was estimated based on the correlation of Barth et al. (21) and
the values of Kp for each amine were estimated using the experimental pKa values.
pKa values were measured using the experimental set-up described in our previous
work (22). Depending upon the order of the reactions, all experimental data for
the studied aqueous cyclic amines were tested with equations (10), (11), or (12).
The equation with the better AAD % (Percentile Absolute Average Deviation) and
R2 was chosen to interpret the mechanism of reactions.
Figure 4. Brnsted correlation of CO2 reaction rates with amines. (data in this
figure was adapted from Rochelle et al. (23))
Both stopped-flow experiment and pKa studies concluded that cyclic amines
are more suitable for CO2 capture than other amines due to their high absorption
rates. Higher second order rate constants for polyamines and cyclic amines mean
that the deprotonation reaction of carbamates was very fast in these amines. By
comparing EDA, AEEA and EEA, it can be observed that the steric hindrance
effect for the reaction kinetics offered by the OH group is greater than the effect
caused by the CH3 group. The order of the reaction increased in the case of
EEA and decreased in the case of AEEA. The temperature sensitivity of the
amine can be noted from the activation energies derived from the rate constants.
Among the amines studied, PZ has the lowest activation energy and EEA has
the highest activation energy. This implies that the highest hindrance effect in
EEA for NH group is the reason for its high activation energy and it decreases
as the hindrance effect is reduced. Two NH groups in PZ contribute to its low
activation energy, indicating that the reaction proceeds very fast by forming
zwitterion ions. Similar conclusion was made by Bishnoi and Rochelle (24) for
the increase in the zwitterion formation rate by a reduction in steric hindrance
around the amine group.
52
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
cyclic amines were found to have fractional reaction order with respect to amine
varying from 1 to 2 (Except PZ). PZ has the highest reaction rate and 1-MPZ the
lowest. The trend of reaction rates are given as (PZ > 2-MPZ > 1-EPZ > 3-MOPA
> HEPZ > 1-MPZ). Aqueous 2-MPZ has an absorption rate similar to aqueous
piperazine, but both PZ and 2-MPZ are solid in nature at room temperature.
54
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
T /K
298.15
303.15
308.15
313.15
Ka (m6 mol2s1)
0.0353
0.0234
0.011
1.296E-14
2.53E-04
3.05E-04
3.47E-04
4.11E-04
KOH-(m6mol2 s1)
1.89E-02
9.20E-03
4.66E-03
4.18E-01
0.961
1.076
1.134
1.028
R2
0.9997
0.9999
1.0000
0.9456
AAD%
1.4
0.8
0.3
1.6
16.7 0.33
18.61 0.21
19.95 0.09
22.65 0.93
R2
0.9896
0.9962
0.9994
0.9447
AAD%
7.5
4.2
1.5
1.7
T /K
298.15
303.15
308.15
313.15
Ka (m6
mol2s1)
0.0259
0.0269
0.026
3.310E-02
Kw (m6
mol2
8.87E-05
1.01E-04
1.19E-04
1.27E-04
4.64E-02
3.33E-05
3.32E-02
2.83E-01
1.231
1.197
1.236
1.252
R2
0.9994
0.9995
0.9995
0.9995
AAD%
1.9
1.8
1.6
1.8
6.90 0.25
7.65 0.26
8.56 0.24
9.55 0.32
R2
0.9675
0.9708
0.9782
0.9717
AAD%
14
13
10
12
KOH-(
s1)
m6mol2
s1)
56
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
T /K
298.15
303.15
308.15
313.15
Ka (m6 mol2s1)
1.50E-10
2.05E-10
2.13E-10
1.23E-10
1.22E-04
1.40E-04
1.59E-04
1.77E-04
4.21E-02
1.92E-02
1.00E-02
1.65E-02
1.066
1.036
1.069
1.084
R2
0.9860
0.9778
0.9821
0.9959
AAD%
5.9
7.4
6.7
7.9
6.74 0.13
7.73 0 .19
8.77 0.19
9.74 0.11
R2
0.9846
0.9760
0.9805
0.9717
AAD%
5.6
7.1
6.5
7.8
T /K
298.15
303.15
308.15
313.15
Ka (m6
mol2s1)
4.43E-02
6.13E-02
1.36E-01
2.09E-01
Kw (m6
mol2
5.78E-05
5.95E-05
9.02E-06
1.38E-11
1.12E-02
3.69E-03
1.07E-02
4.89E-01
1.522
1.389
1.288
1.273
R2
0.9995
0.9995
0.9998
0.9821
AAD%
1.8
1.8
2.2
2.7
k2Z ( m3mol1s1)
(Eq. 11)
12.18 0.52
14.71 0.79
18.23 1.56
23.63 3.09
R2
0.9846
0.9760
0.8906
0.7994
AAD%
19
23
38
59
KOH-(
s1)
m6mol2
s1)
57
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
T /K
298.15
303.15
308.15
313.15
Ka (m6 mol2s1)
4.29E-02
6.49E-02
1.28E-01
0.240
1.52E-04
1.63E-04
1.25E-04
4.45E-05
6.45E-03
1.10E-02
4.29E-03
3.21E-02
2.257
1.880
1.551
1.477
R2
0.9992
0.9995
0.9996
0.9983
AAD%
3.6
2.2
3.7
10.3
k2Z ( m3mol1s1)
(Eq.11)
6.62 0.44
8.03 0.60
11.08 1.35
15.88 2.68
R2
0.9121
0.8936
0.7993
0.7097
AAD%
23
27
51
87
T /K
298.15
303.15
308.15
313.15
Ka (m6 mol2s1)
4.91E-02
4.56E-02
4.88E-02
5.28E-02
5.44E-05
7.51E-05
8.44E-05
9.68E-05
1.00E-02
4.74E-02
7.29E-04
5.96E-04
1.392
1.406
1.418
1.517
R2
0.9993
0.9992
0.9992
0.9992
AAD%
3.9
3.6
3.5
3.4
k2Z ( m3mol1s1)
(Eq.11)
6.89 0.49
7.76 0.46
11.08 1.35
15.88 2.68
R2
0.9121
0.933
0.9357
0.9390
AAD%
36
27
26
25
58
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
pKa
lnKp=A+B/T
T/K
298.15
303.15
308.15
313.15
3-MOPA
9.98
9.73
9.58
9.51
-0.307
-6730
Kp (298.15 K)
1.16E-10
Table 9 lists the order of the reactions, the second order reaction rate constants
and the activation energies of the studied cyclic amines derived by assuming the
rate to be unity. Activation energies and the temperature dependence of the second
order reaction rate constants were calculated using an Arrhenius- relation.
Figure 6 represents the Brnsted-plot for the studied amines at different
temperatures. For all cyclic amines, a linear relationship exists between ln k2 and
pKa. As the pKa increases the second order rate constants for the cyclic amines
decreases. This indicates that the alkalinity of the solution influences the rate of
the reaction between CO2 and the amine. From this plot, the effect of methyl
group (-CH3) can also be observed. The basicity of the piperazine molecule
decreases when it is hindered by the position of methyl group, thereby reducing
the reaction rate with CO2.
59
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Table 9. Second order reaction constants and order of the reaction with CO2
for aqueous cyclic amine solutions
k2Z (m3mol-1s-1) (Eq. 11)
Ea (kJmol-1)
Amine
Order (n)
PZ
0.96 - 1.1
15.24
1-MPZ
1.19 - 1.25
16.85
1-EPZ
1.20 - 1.25
19.10
2-MPZ
1.27 - 1.93
34.13
1.0 - 2
45.61
1.27 - 1.37
44.24
3-MOPA
HEPZ
where [H+],[A-] and [HA] represent the concentrations of the solution species in
molL-1. Then, pKa will be derived as:
60
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
It implies that a solution with 50% dissociation has a pH equal to the pKa of
the acid. For bases, the dissociation constants are reported as pKa values for the
conjugate acid (32):
The basicity of the solvent, quantified by the pKa of its conjugate acid, is a
key factor for the reaction rate and absorption capacity of the solvent in the process
(22). A linear relationship between the pKa of an acid or a base and its reaction rate
was derived by Brnsted et al. (7) In a previous section, a Brnsted relationship
between the rate constant of the reaction of amines with CO2 and the basicity of
such amines was discussed. pKa values of alkanolamines are available in the open
literature at different temperatures (22, 3235). The experimental determination of
the pKa values for five cyclic diamines have been reported in our work at different
temperatures. The experimental set-up and its details were reported in our previous
work (20).
Table 10. First and second pKa values of amines at different temperatures
pKa(1)
T/K
Amine
298
303
313
323
PZ
9.78
9.66
9.39
9.17
2-MPZ
9.57
9.46
9.16
8.97
1-MPZ
9.14
8.99
8.79
8.65
1-EPZ
9.20
9.08
8.93
8.72
HEPZ
9.09
8.95
8.75
8.63
DMPZ
8.38
8.27
8.06
7.84
pKa(2)
T/K
Amine
298
303
313
323
PZ
5.35
5.27
5.02
4.93
2-MPZ
5.24
5.19
4.92
4.84
1-MPZ
4.63
4.40
4.31
4.18
1-EPZ
4.76
4.58
4.48
4.31
HEPZ
3.92
3.89
3.74
3.60
DMPZ
3.81
3.70
3.64
3.45
To sum up and present a clear picture for the change of pKa with the addition
of different radicals to PZ, we suggest the following rules. Starting with the PZ
molecule with two secondary amines, the addition of a methyl group (-CH3) on any
carbon of the ring introduces a hindrance effect and lowers the pKa. The addition
of an ethyl group (CH3-CH2) to PZ further lowers the pKa. The addition of a methyl
group lowers the pKa more than in the case of an ethyl group. The addition of a
hydroxyl group (-OH) to 1-EPZ or a hydroxyl group to PZ reduces the pKa further
than any previous addition (hydrogen bonding). Finally, the addition of a methyl
radical (-CH3) to each secondary amine of PZ to form tertiary amines (DMPZ)
leads to the lowest pKa. These conclusions are valid for the first and second pKa
of the studied amines. In the present study, the calculated S values from the
Vanf Hoff equation were almost negiligible compared to the contribution of the
(H/T) term. The higher the value of H, the larger is the shift in basicity from
low temperature (high basicity leading to better absorption of CO2) to the higher
temperature (low basicity leading to better regeneration of CO2). Accordingly,
2-MPZ and PZ should be the most attractive amines for gas swettening in terms
of cyclic capacity.
62
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Table 11. Experimental pKa values of the bases investigated in our work
Base
Name or Abbreviation
pKa (298.15 K)
Ref
C4H9N2(CH3)
2-methylpiperazine
9.57
(10)
C4H9N2(C2H5)
1-ethylpiperazine
9.20
(10)
C4H9N2(CH3)
1-methylpiperazine
9.14
(10)
C4H9N2(C2H4OH)
1-(2-hydroxyethyl)piperazine
9.09
(10)
C4H8N2(CH3)2
1,4-dimethylpiperazine
8.38
(10)
O(CH2CH2)2NH
morpholine
8.50
(37)
HN(CH2CH2)2NH
piperazine
9.73
(37)
where R is the gas constant and T is temperature. Basicity increases with rG(aq)
and hence with pKa. rG(aq) can be expressed as:
63
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Adam (44) and Tao (45), have found phenomenal accuracy ( 0.2) for a single
class of compounds by taking this approach further, replacing pKa(theo) in equation
(32) with some other computable property of the solute molecule. Of the direct
pKa computation studies (i.e. not based on linear regressions like equation (32),
the few that have reported computed pKa accuracy of better than 1 were studies
of a handful of compounds within a single class and small pKa ranges (4649),
where the slope errors were hard to observe and constant-shift errors might have
cancelled them. A good example would be the work of da Silva et al. (50), whose
results for carboxylic acids looked very good, but whose ensuing results for three
other classes of compounds showed large class-dependent errors (51). Similar
results can be achieved for PZ of pH range 8-11.
5.4. Computational Procedures
All calculations were done using the Gaussian 03 software program
and the 6-311++G** basis set. Solvent effects were computed using the
continuum solvation method IEFPCM (52) with UA0 radii for spherical cavities.
Theelectronic structure levels of theory tested for IEFPCM calculations (including
geometry optimization) were B3LYP and MP2. Geometry optimizations with
IEFPCM minimize Eelec + Gel. All Enuc(0)g@g terms were computed only with
B3LYP at B3LYP gas-phase-optimized geometries. For neutral amine, a hydrogen
atom of the explicit water molecule was hydrogen-bonded to the nitrogen atom in
amine, while for protonated amine the new proton attached to nitrogen atom was
hydrogen-bonded to the oxygen of water molecule. The use of one explicit water
molecule was named as Model II, to distinguish from Model I, where no explicit
water is used. The utility of a constant scale factor to contract the radii of charged
united atoms was tested to accommodate electrostriction. Instead of the default
64
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
factor of 1.0 for the NHx groups of protonated amines, 0.9 was used. This was
referred to as special scaling. Conformer choices and entropy calculations are
explained in our previous work (10). The conformers used were the ones with
lowest in energy from IEFPCM/B3LYP calculations.
B3LYP
Model I
B3LYP
Model II
MP2
Model II
B3LYP
Model II
MP2
Model II
Base
Ref (9)
Def. sc.a
Sp. sc.a
Sp. sc.a
Def. sc.a
Def. sc.a
exptb
morpholine
10.97
9.61
9.21
8.97
9.81
9.56
8.50
piperazinec
12.49
12.21
11.26
10.87
12.02
11.61
9.73
rms error
1.79
1.85
1.47
1.30
1.22
1.00
Def. sc. means default radii scaling, Sp. sc. means special scaling;
see Table 11; c pKa(1)
For references
65
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
MP2
B3LYP
MP2
Expta
Morpholine
9.13
9.04
7.65
7.89
8.50
Piperazineb
11.34
11.10
9.86
9.95
9.73
2-methylpiperazineb
11.01
10.46
9.53
9.31
9.57
1-ethylpiperazineb
10.95
10.60
9.47
9.45
9.20
1-methylpiperazineb
10.40
10.02
8.92
8.87
9.14
1-(2-hydroxyethyl)piperazineb
10.49
10.08
9.01
8.93
9.09
1,4-dimethylpiperazineb
10.65
10.37
9.17
9.21
8.38
1.48
1.18
0.81
0.68
Base
rms error
a
two fitting
parameters
pKa(1)
6. Conclusion
Screening of primary, secondary, poly and cyclic amines was performed using
a stopped-flow technique at 298.15 K over a concentration range of (20 to 120)
molm-3. Polyamines and cyclic amines have higher pseudo first order reaction
rates compared to linear secondary and primary amines. Consequently, six
cyclic amines were studied between (298.15 and 313.15) K over a concentration
range of (20 to 120) molm-3. PZ had the highest reaction rate and 1-MPZ the
lowest. At the same temperature, the trend of reaction rates is given as (PZ >
2-MPZ > 1-EPZ > 3-MOPA > HEPZ > 1-MPZ). The termolecular mechanism
was used for calculating the rate parameters by fitting the experimental data.
Higher second order rate constants for polyamines and cyclic amines mean that
the deprotonation reactions of carbamates were very fast for these amines. The
dissociation constants of the conjuagate acids of six cyclic diamines (PZ, 1-MPZ,
2-MPZ, 1-EPZ, HEPZ and DMPZ) were meaured using a potentiometric titration
method at (298, 303, 313 and 323) K. A trend is proposed relating the variation
of pKa with the addition of different radical groups to the base PZ molecule. pKa
values of piperazines were computed using quantum chemistry techniques and
the IEFPCM continuum solvation model. Of several techniques tested, the best
one involved the incorporation of an explicit water molecule inside the continuum
cavity (Model II). Proper entropy corrections, often neglected in pKa studies,
were also included. The use of a second fitting parameter for these compounds
dramatically lowered the overall rms error by 42-45%. Our best technique
reduced the errors found in a previous technique (9) for similar compounds by
62% (10).
66
In Recent Advances in Post-Combustion CO2 Capture Chemistry; Attalla, M.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
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